Insect repellent method and composition



United States Patent 2,824,822 INSECT REPELLENT METHOD AND COMPOSITIONLyle D. Goodhue, Bartlesvilie, and Kenneth E. Cantrel,

Dewey, kla., assignors to Phillips Petroleum Company, a corporation ofDelaware No Drawing. Application June 221, i955 Serial No. 517,054 20Claims. (Cl. 167-22} This invention relates to repelling of insects andto compositions for repelling insects. In one aspect the inventionrelates to an improved insect repellent composition comprising a ternarymixture comprising first, at least one di-n-alkyl ester of adicarboxylic acid of pyridine wherein the alkyl groups contain from 2 to4 carbon atoms; second, at least one 1-acetoxy-3-phenyl-2- alkenewherein the alkene is a normal alkene having from 3 to 4 carbon atoms;at least one N-alkyl imide of bicyclo[2.2.l]-5-heptene-2,3-dicarboxylicacid wherein the alkyl radical contains not more than 12 carbon atoms.In another aspect the invention relates to a method of repellinginsects, for example, stable files, by applying a composition, as setforth herein, at a locus from which the insect is to be repelled.

It is an object of the invention to provide an improved insect repellentcomposition. It is another object of the invention to provide animproved method of repelling insects. A particular advantage of ourrepellent composition of three components is that the said compositionexhibits longer effective repellent life than any combination of two ofthe three components, or than any one of the three materials. Thisincrease in the effective life of the repellent composition is sometimesreferred to as synergism in this application.

Other objects, as well as aspects and advantages of the invention areapparent from this disclosure and the appended claims.

The diethyl, di-n-propyl and di-n-butyl esters of a dicarboxylic acid ofpyridine are known to be effective as agents for repelling housefiies,stable flies, and other in sects from surfaces frequented by the insectswhen the compounds are applied to such surfaces, as set forth andclaimed in application Serial No. 240,602, of N. J. Leonard, filedAugust 6, 1951, now Patent No. 2,757,120. The fly repelling activity ofthese esters is known to be synergized by the incorporation of N-alkylimides of bicylo [2.2.1]-5-heptene-2,3-dicarboxylic acid, as disclosedand claimed in application Serial No. 453,122, of Goodhue et a1., filedAugust 30, 1954.

An improved insect repellent composition containing at least one ofdiethyl, di-n-propyl and di-n-butyl esters of pyridine dicarboxylic acidand at least one of .l-acetoxy- 3-phenyl-2-butene and1-acetoxy-3-phenyl-2-propene is disclosed and claimed in applicationSerial No. 515,237 of Lyle D.'Goodhue, filed June 13, 1955, acontinuation- :in-part of Serial No. 419,110, filed March 26, 1954, now

abandoned.

Serial No. 640,337, filed February 15, 1957, a continuation-in-part ofSerial No. 436,706, now abandoned, filed June 14, 1954, discloses andclaims, among other things, an insect repellent composition comprising1- acetoxy-B-phenyl-Z-butene in an adjuvant and a method for repellingan insect comprising applying at the place from" which the insect is tobe repelled, a repellent quantity. 'of l-acetoxy-3-phenyl-2-butene.

We have now found that a mixture comprising the three components setforth hereinbefore as the essential active repellent composition has alonger effective life thany any one of the components alone or in anymixture of only two of such components. Thus, according 2,824,822Patented Feb. 25,1958

to our invention, we have provided a ternary stable fly repellentcomposition comprising:

(1) At least one di-n-alkyl ester of a carboxylic acid of pyridinewherein the alkyl groups contain from 2 to 4 carbon atoms,

(2) At least one l-acetoXy-3-phenyl-2-alkene wherein the alkene is analkene having from 3 to 4 carbon atoms, and

(3) At least one N-alkyl imide of bicyclo[2.2.1]-5-heptene-,2,3-dicarboxylic acid wherein the alkyl radical contains notmore than 12 carbon atoms, as the essential active repellent.

The proportion in which these compounds are present in the compositioncan vary. It is now preferred that the alkyl imide ofbicyclo[2.2.ll5-heptene-2,3-dicarboxylic acid is present in the amountin the range from 25 to weight percent of the ternary mixture, on anundiluted basis and that the other two components be present in theternary composition in a ratio in the range from 4:1 to 1:4 of thepyridine dicarboxylate to the 1-acetoxy-3-phenyl-2-alkene. Ternarycompositions outside these ranges can be employed.

The ternary composition can be applied to the desired surfaces in anysuitable form, such as a solution in a mutual solvent, as an emulsion,aerosol, fog, and the like, and in any suitable manner, as by spraying,brushing, dipping, and the like. Application, according to theinvention, can be effected by first applying one of the ingredients ofthe mixture and then applying another, and so on. For best and nowpreferred results, in any event, the compositions, as applied, are madeup to contain a repellent adjuvant to dilute the active ingredients toan effective, but not undesirably high, concentration. Solvents,diluents, or other adjuvant carriers which are applicable includeacetone, hydrocarbons such as kerosene,

naphthas, and other liquid hydrocarbons. The now preferred solvent is anisoparafiinic hydrocarbon having a boiling range of approximately 260 to800 F. Powders or dusts such as, for instance, talc are also sometimesused as the adjuvant carrier. Though not presently preferred, therepellent composition can be employed without a carrier, if desired.

When an adjuvant carrier or solvent is employed in conjunction withthese ternary repellent compositions, the repellent composition willgenerally be in the concentration of 0.3 to 30 Weight percent of thecarrier material. It is now preferred that the range is from 0.5 to 15weight percent of the carrier material.

In general, it is suficient to deposit about 0.01 to 5 grams per squarefoot of surface, preferably in the range of 0.1 to 3 grams per squarefoot, although larger or smaller amounts can be employed.

While the ternary fly repellent composition is particularly efiective asa stable fly (Stomoxy calcitrans) repellent, it is also effective forrepelling house flies (Musca domestica)- Representative examples of theN-alkyl imides of bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid includeN- methyl bicyclo[2.2.1]-5-heptene-2,S-dicarboximide; N- ethyl bicyclo[2.2.1 ]-5-heptene-2,3-dicarboximide; N-isopropyl bicyclo[2.2.1]-5-heptene-2,3-dicarboximide; N-Z- ethylhexylbicyclo[2.2.1]-5-heptene 2,3 dicarboximide; N-t-dodecyl bicyclo [2.2. l1 -5-heptene-2,3 dicarboximide; N-isoheptyl bicyclo[2.'2.1l-5-heptene2,3 dicarboximide; N-t-butyl bicyclo[2.2.1]-5-heptene-ZJ-dicarbQYimide;N- 3-propyloctyl bicyclo [2.2. l J -5-heptene-2,3-dicarb oximide;N-2,3-dimethyldecyl bicyclo[2.2.ll-5-heptene 2,3 dicarboximide, andN-octyl bicyc1o[2.2.1]-5-heptene-2,3-dicarboximide.

Examples of the esters of pyridine dicarboxylic acids include thedi-n-propyl ester of pyridine-3,4-dicarboxy1ic acid, the diethyl esterof pyridine-3,idicarboxylie acid, the diethyl ester ofpyridine-2,S-dicarboxylic acid, the din-propyl ester ofpyridine-2,S-dicarboxylic acid, the di-nbutyl ester ofpyridine-2,5-dicarboxylic acid, the diethyl ester ofpyridine-2,6-dicarboxylic acid, the 'di-n-propyl ester, of -pyridine-2,6diarboxylic acid, the di -n-propyl esterof pyridine-2,4-dicarboxylicacid; the dithyl ester of pyridine-2,4-dicarboxylic acid, thedi-n-propyl ester of i 'pyridine-2,3;diearboxylic acid, andthe diethylester of pyridine-2,3-diearboxylic acid. Of the pyridine dicarboxylicacid diesters those of pyridine-2,5-dicarboxylic acid arenowpreferred,"especially the d i-n-propyl ester of pyridine 2,5dicarboxylic acid. I

'Repellency and synergism of compositions of. this in- "vention weredemonstrated by the organdy' bagmethod inthe following examples;

Qrgandy bags having IOO s quare inches of area were impregnated with sixto severi milliliters of acetone that contained the repellent materialto be tested. As the life V of a colony of stable flies is oftenexceeded by the repel lent life of a fly-repellentcomposition, theimpregnated bags were hung on a line and were tested after a waitingperiod which ranged from one to seven days. The repellents were thentested by exposing the hand to hungrystable flies through theimpregnated organdy bags. The stable fly colony was not fed for severalhours so that they would be hungry, and the number o f flies present Waskept at a high leyel so that at least one was attempting to bite eachsecond. The period of effective repellency was recorded as the time fromthe day on which the bags were impregnated to the day on which the firstbite was sustained. This recorded effective repellency period 7 is thusone of 100 percent repellency. The results of this test are expressedbelow in Table I. I V

The 1-acetoxy-3-phenyl-2-butene used in this example was a distillationcut of boiling range 95-100" C.jat 0.8 .mm. Hg taken from a reactionmixture prepared in the ,following manner. 330 grams 10.9 moles) ofparaformaldehyde, 1180 grams (10 moles) of u-methyl-styren e, 2250milliliters of glacial acetic acid, and 3.6 millili ters of sulfuricacid (conc.) were fed to a reactor and reacted for three hours bystirring at 35 C. During this period the temperature rose; to 45 C., butwas lowered Distillation cuts were then taken from the pot residue.

The over-all boiling range of'the reaction mixture was s 55 p py y855-114.? C., at 0.8 mm. Hg.

Table I Compound No. Name 1 Di-n-propyl ester of pyridine-2,5-dlcarboxylic acid. 2 1-acct0xy-3-Dheuyl-2-buteue. 5 3 Nigctylbtcycloheptene dicarboxlme. H w

Run #1-Each Component Alone: r t r r Grams per Bag Days Repellent 1;2.0-- 1 '9 V 2.0 4 3 9 3 Run#2 Binary Combinations:

1 and 2 1.0 gram of each 4 1and3 n n r V 2 r '2and3. d 7

Run #3 Ternary Combination: T p p 0.5 of compound 1- 1, 2, and 3 0 ofcompound 2 j 13 t t 1.0 of compound 3.2",

These data show clearly the synergism exhibited by the ternarycomposition. It is seen that the ternary composition has a longereffective repellent life than any combination of two of the threematerials, or than any one of 5 the three materials alone;

Aslwill be evident to thoseslkilled'in the art, various modifications ofthis invention canbe' made 'or followed in the lightot the foregoingdisclosure anddiscussion without departing from the spirit or scope ofthe; disclosure or from the scope of the claims. j I

Weclaim:

l. A ternary synergistic repellent composition compris- 1 'ing thefollowing three components as the essential active repellentcomposition: (a) at least one di-n-alkyl ester of 15 a dicarboxylic acidof pyridine wherein the alkyl groups contain from 2 to 4 carbon atoms;(b at least one l -acetvoxy-li-phenyl-2-alkene wherein QtheaIkene is analkcne I having from threeto four carbon atoms, -and (c);at-least "oneN-alkyl imide of:bicyclo[2.2.1] 5-heptene-2,3-dicarboxylic acid whereinthealkyl radical contains not more than 12 carbon atoms, wherein saidalkyl imide is present,

in the ternary composition in an amount in the range; from fto 75'percent,.ion an undiluted basis of said ternary composition and theratio of; said ester of said pyridine ,carboxylic acid to said1-acetoxy-3-phenyl-2-alkene isj Qthc range from 4:1 to 1:4. 7

-*2.' The composition of claim 1 'wherein'thesaid ester is' an ester ofpyridine-2,5-dicarboxylic acid.

3. The composition of claim 1 wherein the saidl-acetfoxy-3-phenyl-2-alkene is 1-acetoxy-3-phenyl-2-butene.

f 4E :Thecomposition of claim 1 wherein the'said l-acetoxy-3-phenyl-2-alkenej is 1-acetoxy-3 phenyl-2-propene. I V V 5. The composition ofclaim z wherein the said 'l-acetoxy-3-phenyl-2-2tlkene is 1-acetoxy-3-phenyl-2-butene.

7. The composition of claim 5 wherein thesaidester is the di-n-propylester of pyridine-.2,S-dicarboXylic acid and said alkyl imide isN-octyl,bicycloi[2.2.l]-5-heptene- 2,3-dicarboximide. 'i' .tf

8. The composition of claim'S wherein the 'said' ester is the diethylester of pyridine-2,5-dicarboxylic-.acid. a:

' 9. The composition of claim 5 wherein the said 'esteris the di-n butylesterof pyridine-2,5-dicarboxylicacid; I;-

- l0.' The composition of claim 1 whereinrthelsaidflalkyl imide isselected from the group'consisting ofzN- methyl"bicyclo[2.2.1]-5-heptenee2,3-dicarboximide; .-N- r ethyl bicyclo [2.2.1-5-heptene-2,3-dicarboximide} N-iso- .propyl bicyclo 2.2.1]-5-heptene-2,3:dicarboximidej iN-Z-i ethylhexyl bicyclo [2.2. l-5-heptene-2,3-dicarboximidc; N- V 't-dodecylbicyclo[2.2.1l-5-heptene-2,3-dicarboximide; N-

isoheptyl bicyclo[2.2.1]-5-heptene-2,3-dicarboximide; N-

t-butyl bicyclo[2.2.1 1 -5-heptene-2,3 dicarboximide; N-3-N-2,3-dimethyldecyl V boximide, and N-octyl bicyclo[2.2.1l-5-heptene-2,3dicarboximide.

' 11. The composition of claim 1 in a suitablesolventfor 6 0 saidrepellent. r

12. A method of rendering a surface repellent ito flies 'whichcomprisesapplying to said surface a composition of claim 1.

, '13: The composition of claim 1 wherein the. said N- alkyl'imide isN-octyl bicyclo[2.2.1] 5-heptene-2;3 di- *carboximide. a The compositionof claim 1 wherein thesaidN- alkyl imide is N-2-ethylhexylbicyclo[2.2.11-5-hcptenc- 2,3-dicarboximide.

'iO- 15. The compositionof claim 1 wherein the saidN- alkyl imide isN-t-butyl bicyclo[2.2.1 '5heptene-2,3.diwarboximide. e

r 6. The composition of claim 2 wherein the said l-ace' t- V Aoxy-3-phenyl-2-alkene' is 1-acetoxy-3-phenyl-2 propene.i

bicyclo [2.2. 1 -5.-heptene-2, 3 dicarboxirnide;'

bicyclo [2.2. l -5-heptene-2,3-dicar- 17. The composition of claim 1wherein the said N- alkyl imide is N-t-dodecylbicyclo[2.2.1]-5-heptene-2,3- dicarboximide.

18. A ternary synergistic repellent composition comprising the followingthree components as the essential active repellent composition: (a) thedi-n-propyl ester of pyridine-2,S-dicarboxylic acid,(b)l-acetoxy-3-phcnyl-2- butene, and (c) at least one N-alkyl imide ofbicycle- [2.2.1]-5-heptene-2,3-dicarboxy1ic acid wherein the alkylradical contains not more than 12 carbon atoms, wherein said alkyl imideis present in the ternary composition in an amount in the range from 25to 75 percent, on an undiluted basis of said ternary composition and theratio of said ester of said pyridine carboxylic acid to saidl-acetoxy-3-phenyl-2-butene is in the range from 4:1 to 1:4.

19. A method of repelling flies which comprises subjecting the locusfrom which the insect is to be repelled to the action of a compositionof claim 18.

20. The composition of claim 18 wherein the said N- 6 alkyl imide isN-Z-ethylhexyl bicyclo [2.2.1 ]-5-heptene-2,3- dicarboximide.

References Cited in the file of this patent UNITED STATES PATENTS2,043,941 Williams June 9, 1936 2,424,220 Bousquet July 22, 19472,757,120 Leonard July 31, 1956 OTHER REFERENCES Drake et al.: Abstr. ofSer. No. 70,392, pub. January 9, 1951.

Prostenik et al.: Archiv. Kemi, vol. 18, pp. 3-9, 1946 (Chem. Abstr.,vol. 42, 3398 C., 1948).

OSRD Insect Control Comm. Rpt. No. 28, Interim Rpt. No. 0-94, May 18,1945. Pub. August 1, 1947, 50 pp. plus 1 p. of index, part. p. 27,Orlando No. 0-2333, Pyridine-2,3 dicarboxylic acid, dimethyl ester, andpp. 1-4, 9, 16 and 21 for methods of using the repellents.

1. A TERNARY SYNERGISTIC REPELLANT COMPOSITION COMPRISING THE FOLLOWINGTHREE COMPONENTS AS THE ESSENTIAL ACTIVE REPELLANT COMPOSITION: (A) ATLEAST ONE DI-N-ALKYL ESTER OF A DICARBOXYLIC ACID OF PYRIDINE WHEREINTHE ALKYL GROUPS CONTAIN FROM 2 TO 4 CARBON ATOMS, (B) AT LEAST1-ACETOXY-3-PHENYL-2-ALKENE WHEREIN THE ALKENE IS AN ALKENE HAVING FROMTHREE TO FOUR CARBON ATOMS, AND (C) AT LEAST ONE N-ALKYL AMIDE OFBICYCLO(2.2.1)-5-HEPTENE-2,3-DICARBOXYLIC ACID WHEREIN THE ALKYL RADICALCONTAINS NOT MORE THAN 12 CARBON ATOMS, WHEREIN SAID ALKYL AMIDE ISPRESENT IN THE TERNARY COMPOSITION IN AN AMOUNT IN THE RANGE FROM 25 TO75 PERCENT, ON AN UNDILUTED BASIS OF SAID TERNARY COMPOSITION AND THERATIO OF SAID ESTER OF SAID PYRIDINE CARBOXYLIC ACID TO SAID1-ACETOXY-3-PHENYL-2-ALKENE IS IN THE RANGE FROM 4:1 TO 1:4: